Method for the use of slurries in spray pyrolysis for the production of non-hollow, porous particles

Patent metadata

Field	Value
Publication number	US-9748567-B2
Application number	US-201414775231-A
Country	US
Kind code	B2
Filing date	Mar 13, 2014
Priority date	Mar 13, 2013
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

A process for preparing a metal oxide-containing powder that comprises conducting spray pyrolysis that comprises aerosolizing a slurry that comprises solidphase particles in a liquid that comprises at least one precursor compound, which comprises one or more metallic elements of at least one metal oxide, to form droplets of said slurry, and calcining the droplets to at least partially decompose the at least one precursor compound and form the metal oxide-containing powder having a non-hollow morphology.

First claim

What is claimed is:

1. A process for preparing a metal oxide-containing powder, the process comprising conducting spray pyrolysis that comprises:
(a) aerosolizing a slurry that comprises solid-phase particles in a precursor solution to form droplets that comprise the precursor solution and one or more of the solid-phase particles, wherein (i) the solid-phase particles have a mean size that is in a range of about 10 nm and 50 μm, and (ii) the precursor solution comprises at least one precursor compound dissolved or suspended in a solvent, wherein the at least one precursor compound comprises one or more metallic elements of at least one metal oxide, and (iii) the slurry has a total mass fraction of solid-phase particles to metal oxide-containing powder that is in a range of about 2% to about 75%;
(b) evaporating the solvent in the droplets to form dried droplets that comprise the at least one precursor compound and one or more solid-phase particles; and
(c) calcining the dried droplets to at least partially decompose the at least one precursor compound and form the metal oxide-containing powder, wherein the metal oxide-containing powder comprises product particles that comprise the at least one metal oxide, wherein the product particles have (i) a mean size that is in a range of about 100 nm to about 500 μm and (ii) a mean hollowness, which is less than a mean hollowness of particles of about the same mean size prepared by an otherwise identical spray pyrolysis process conducted except for the absence of seed particles in the aerosol.

2. The process of claim 1 , wherein the mean size of the solid-phase particles is in the range of about 100 nm to about 15 μm, and the mean size of the product particles is in the range of about 500 nm to about 50 μm.

3. The process of claim 1 , wherein the mean hollowness of the product particles is less than about 20%.

4. The process of claim 1 , wherein the solid-phase particles are selected from the group consisting of (i) decomposing solid-phase particles that have a composition that decomposes during the calcining, (ii) stable solid-phase particles that have a composition that does not substantially decompose during the calcining solid-phase particles, (iii) partially stable solid-phase particles that have a composition that comprises at least one compound that decomposes during the calcining and at least one different compound that does not substantially decompose during the calcining, and (iv) combinations thereof.

5. The process of claim 1 , wherein the solid-phase particles have a non-hollow morphology.

6. The process of claim 1 , wherein the product particles further have (iii) a porous morphology.

7. The process of claim 1 further comprising annealing the product particles to further decompose the at least one precursor compounds, cause crystallite growth, or both, and
cooling the annealed product particles at a rate sufficiently slow so as to inhibit formation of defects in the at least one metal oxide.

8. The process of claim 1 , wherein substantially all of the product particles have a substantially uniform composition.

9. The process of claim 1 , wherein substantially all of the product particles have a non-uniform composition, wherein the solid-phase particle portion(s) thereof are of a different composition than that of the at least one metal oxide portion thereof.

10. The process of claim 1 , wherein the solid-phase particles are selected to promote nucleation of the at least one metal oxide.

11. The process of claim 1 , wherein the solid-phase particles and the at least one metal oxide are independently selected to have a general chemical formula
Li 1+α (Ni x Co y Mn z ) 1−t M t O 2−d R d , wherein:
M is selected from a group consisting of Al, Mg, Fe, Cu, Zn, Cr, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si, Ti, Zr, and mixtures thereof;
R is selected from a group consisting of F, Cl, Br, I, H, S, N, and mixtures thereof; and
0≦α≦0.50; 0<x≦1; 0≦y≦1; 0<z≦1; 0≦t≦1; and 0≦d≦0.5.

12. The process of claim 11 , wherein the precursor solution comprises at least two precursor compounds, which are selected such that when combined in the precursor solution they decompose at temperatures within about 300 ° C. of each other and that are below the evaporation temperature for the metallic elements of the metal oxide.

13. The process of claim 12 , wherein the precursor solution comprises LiNO 3 , Mn(NO 3 ) 2 , and Ni(NO 3 ) 2 and/or hydrates thereof.

14. The process of claim 12 , wherein the precursor solution comprises LiNO 3 , Mn(NO 3 ) 2 , Ni(NO 3 ) 2 , and Co(NO 3 ) 2 and/or hydrates thereof.

15. The process of claim 11 , wherein the product particles are mesoporous secondary particles with a mean size in the range of about 1 μm to about 15 μm that comprise metal oxide primary particles having a mean size in the range of about 50 nm to about 500 nm.

16. The process of claim 1 , wherein the solid-phase particles and the at least one metal oxide are independently selected to have a composite chemical formula xLi 2 MO 3 *(1−x)LiM′O 2 wherein:
M is one or more metallic ions having an average oxidation state of +4;
M′ is one or more metallic ions having an average oxidation state of +3; and
0<x<1.

17. The process of claim 16 , wherein M is Mn and M′ is selected from the group consisting of Mn, Ni, Co, and combinations thereof.

Assignees

• Univ Washington

Inventors

• Elhassid Dror
• Moller William
• Axelbaum Richard
• Lengyel Miklos
• Atlas Gal

Classifications

• C01D15/02

  Oxides; Hydroxides · CPC title

• C01P2004/03

  obtained by SEM · CPC title

• C01G51/42

  containing alkali metals, e.g. LiCoO2 · CPC title

• C01P2004/82

  two phases having the same anion, e.g. both oxidic phases · CPC title

• C01G45/1228

  of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2 · CPC title